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CpRu-Catalysis in enantioselective decarboxylative allylic substitutions and reactions of α-carbonyl diazo compounds

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Defense Thèse de doctorat : Univ. Genève, 2010 - Sc. 4259 - 2010/10/19
Abstract The aim of this PhD work was the study of CpRu-moieties as catalysts for allylic substitution processes. It was shown that [CpRu(CH3CN)3][PF6] or [CpRu(?6-naphthalene)][PF6] in combination with a pyridine oxazoline ligand efficiently catalyze the decarboxylative allylic rearrangement of allyl aryl carbonates. Good levels of regio- and enantioselectivity were obtained. Starting from enantioenriched secondary carbonates, the reaction is stereospecific and the corresponding allylic ethers are obtained with net retention of configuration. Moreover, conditions were found to apply this methodology to “classical” intermolecular etherifications using allyl alkyl carbonates as substrates and phenols as reactants. The reactivity of complex [CpRu(CH3CN)3][PF6] with diazo acceptor/acceptor moieties is also presented. Interestingly, in presence of Lewis basic molecules, this interaction results into cycloadditions and C-X insertions in particular. Using this strategy, attempts to generate non-racemic dioxoles are described. Finally a new reactivity of the Ru-carbene intermediates was discovered; these species undergoing C-H insertion in the presence of tetrahydrofuran moieties.
Keywords Allylic compoundsα-diazo carbonyl compoundsEnantioselective catalysisRu-Catalyst
Stable URL https://archive-ouverte.unige.ch/unige:12514
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URN: urn:nbn:ch:unige-125143
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Deposited on : 2010-11-17

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